Intensification of Ethyl Esters Synthesis Using a Packed-Bed Tubular Reactor at Supercritical Conditions
Authors: Camila da Silva, Simone Belorte de Andrade, Vitor Augusto dos Santos Garcia, Vladimir Ferreira Cabral, J. Vladimir Oliveira Lúcio Cardozo-Filho
Abstract:
In the present study, the non-catalytic transesterification of soybean oil in continuous mode using supercritical ethanol were investigated. Experiments were performed in a packed-bed tubular reactor (PBTR) and variable studied were reaction temperature (523 K to 598 K), pressure (10 MPa to 20 MPa), oil to ethanol molar ratio (1:10 to 1:40) and water concentration (0 wt% to 10 wt% in ethanol). Results showed that ethyl esters yields obtained in the PBTR were higher (> 20 wt%) than those verified in a tubular reactor (TR), due to improved mass transfer conditions attained in the PBTR. Results demonstrated that temperature, pressure, oil to ethanol molar ratio and water concentration had a positive effect on fatty acid ethyl esters (FAEE) production in the experimental range investigated, with appreciable reaction yields (90 wt%) achieved at 598 K, 20 MPa, oil to ethanol molar ratio of 1:40 and 10 wt% of water concentration.
Keywords: Packed bed reactor, ethyl esters, continuous process, catalyst-free process.
Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1127569
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[1] T. Pinnarat, P. Savage, “Assessment of noncatalytic biodiesel synthesis using supercritical reaction conditions,” Ind. Eng. Chem. Res, vol. 47, pp. 6801-6808, 2008.
[2] D. Wen, H. Jiang, K. Zhang, K, “Supercritical fluids technology for clean biofuel production,” Prog. Nat. Sci, vol. 19, pp. 273-284, 2009.
[3] H. Imahara, E. Minami, S. Hari, S. Saka, “Thermal stability of biodiesel in supercritical methanol,” Fuel, vol. 87, pp. 1-6, 2007.
[4] I. Vieitez, C. Silva, I. Alkimim, F. Castilhos, J.V. Oliveira, M.A. Grompone, I. Jachmanián, “Stability of ethyl esters from soybean oil exposed to high temperatures in supercritical ethanol,”J. Supercrit. Fluid, vol. 56, pp. 265–270, 2011.
[5] P. Olivares-Carrillo, J. Quesada-Medina, “Synthesis of biodiesel from soybean oil using supercritical ethanol in a one-step catalyst-free process in batch reactor”J. Supercrit. Fluid., vol. 58, pp. 378-384, 2011.
[6] H. Shin, S. Lim, S.Bae, S.C. Oh, “Thermal decomposition and stability of fatty acid methyl esters in supercritical methanol,”J. Anal. Appl. Pyrol., vol. 92, pp. 332–338, 2011.
[7] G. Anitescu, A. Deshpande, L.L.Tavlarides, “Integrated technology for supercritical biodiesel production and power cogeneration,”Energy & Fuel, vol. 22, pp. 1391-1399, 2008.
[8] N. Aimaretti, D.I. Manuale, V.M.Mazzieri, C.R. Vera, C.Yori, “Batch Study of Glycerol Decomposition in One-Stage Supercritical Production of Biodiesel,”Energy & Fuel,vol. 23, pp. 1076-1080, 2009.
[9] N.S. Kasim, T.H. Tsai, S.Gunawan, Y.H.Ju, “Biodiesel production from rice bran oil and supercritical methanol,”Bioresour. Technol.,vol. 100, pp. 2007–2011, 2009.
[10] V.F. Marulanda, G.Anitescu, L.L.Tavlarides, “Investigations on supercritical transesterification of chicken fat for biodiesel production from lowcost lipid feedstocks,”J. Supercrit. Fluid.,vol. 54, pp. 53–60, 2010.
[11] D. Kusdiana, S. Saka, “Biodiesel fuel from rapeseed oil as prepared in supercritical methanol,”Fuel,vol. 80, pp. 225-231, 2001.
[12] E. Minami, S. Saka, “Kinetics of hydrolysis and methyl esterification for biodiesel production in two-step supercritical methanol process,”Fuel,vol. 85, pp. 2479-2483, 2006.
[13] H. He, W. Tao, S. Zhu, “Continuous production of biodiesel from vegetable oil using supercritical methanol process,”Fuel,vol. 86, pp. 442-447, 2007.
[14] C. Silva, T.A. Weschenfelder, S. Rovani, F.C. Corazza, M.L. Corazza, C. Dariva, J.V. Oliveira, “Continuous production of fatty acid ethyl esters from soybean oil in compressed ethanol”Ind. Eng. Chem. Res.,vol. 46, pp. 5304-5309, 2007.
[15] I. Vieitez, M.J. Pardo, C. Silva, C.Bertoldi, F. Castilhos, J.V.Oliveira, M.A. Grompone, I. Jachmanián, “Continuous synthesis of castor oil ethyl esters under supercritical ethanol,”J. Supercrit. Fluid., vol. 56, pp. 271–276, 2011.
[16] W. Cao, H. Han, J. Zhang, “Preparation of biodiesel from soybean oil using supercritical methanol and co-solvent,”Fuel,vol. 84, pp. 347-351, 2005.
[17] P.Hegel, G.Mabe, S.Pereda, E.A.Brignole, “Phase transitions in a biodiesel reactor using supercritical methanol,”Ind. Eng. Chem. Res.,vol. 46, pp. 6360-6365, 2007.
[18] J.Z. Yin, M. Xiao, J.B. Song, “Biodiesel from soybean oil in supercritical methanol with co-solvent,”Energy Convers. Manag., vol. 49, pp. 908-912, 2007.
[19] C. Bertoldi, C. Silva, J.P. Bernardon, M.L. Corazza, L. Cardozo Filho, J.V. Oliveira, F.C. Corazza, “Continuous Production of Biodiesel from Soybean Oil in Supercritical Ethanol and Carbon Dioxide as Co-solvent,” Energy & Fuels, vol. 23, pp. 5165-5172, 2009.
[20] C.M. Trentin, A.P. Lima, I.P. Alkimim, C. Silva, F. Castilhos, M.A. Mazutti, J.V. Oliveira, “Continuous catalyst-free production of fatty acid ethyl esters from soybean oil in microtube reactor using supercritical carbon dioxide as co-solvent,”J. Supercrit. Fluid.,vol. 56, pp. 283-291, 2011.
[21] S.A. Ippolito, J.C.Yori, M.E.Iturria, C.L.Pieck, C.R. Vera,“Analysis of a two-step, non-catalytic, supercritical biodiesel production process with heat recovery,”Energy & Fuels,vol. 21, pp. 339-346, 2007.
[22] C. Silva, A.P Lima, F. Castilhos, L. Cardozo Filho, J.V. Oliveira, “Non-catalytic production of fatty acid ethyl esters from soybean oil with supercritical ethanol in a two-step process using a microtube reactor,”Biomass Bioenerg, vol. 35, pp. 526-532, 2011.
[23] D. Kusdiana, S. Saka, “Two-step preparation for catalyst-free biodiesel fuel production,”Appl. Biochem. Biotechonol.,vol. 113, pp. 781-791, 2004.
[24] C. Chen, W. Chen, C.J. Chang, S. Lai, C. Tu, “Biodiesel production from supercritical carbon dioxide extracted Jatropha oil using subcritical hydrolysis and supercritical methylation,”J. Supercrit. Fluid,vol. 52, pp. 228–234, 2010.
[25] C. Silva, F. Castilhos, J.V. Oliveira, L. Cardozo Filho, “Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor,”Fuel Process.Technol., vol. 91, pp. 1274-1281, 2010.
[26] C.M. Trentin, A.P. Lima, I.P. Alkimim, C. Silva, F. Castilhos, M.A. Mazutti, J. V. Oliveira, “Continuous production of soybean biodiesel with compressed ethanol in a microtube reactor using carbon dioxide as co-solvent,”Fuel Process.Technol.,vol. 92, pp. 952-958, 2011.
[27] E. Achenbach,“Heat and Flow Characteristics of Packed Beds,”Exp. Therm. Fluid. Sci.,vol. 10, pp. 17-27, 1994.
[28] Y. Su, “The Intensification of Rapid Reactions for Multiphase Systems in a Microchannel Reactor by Packing Microparticles,”AIChE J.,vol. 57, pp. 1409–1418, 2011.
[29] F. Ataya, M.A. Dube, M. Ternan, “Transesterification of Canola Oil to Fatty Acid Methyl Ester (FAME) in a Continuous Flow Liquid-Liquid Packed Bed Reactor,”Energy & Fuels,vol. 22, pp. 3551–3556, 2008.
[30] Standard UNE-EN 14103,“Determination of ester and linolenic acid methyl ester contents, issued by Asociación Española de Normalización y Certificación,” Madrid, 2003.
[31] K.T. Tan, K.T., Lee, A.R. Mohamed, “Production of FAME by palm oil transesterification via supercritical methanol technology,”Biomass Bioenerg.,vol. 33, pp. 1096-1099, 2009.
[32] M.M. Gui, K.T. Lee, S. Bhatia, “Supercritical ethanol technology for the production of biodiesel: process optimization studies,”J. Supercrit. Fluid., vol. 49, pp. 286-292, 2009.
[33] R. Sawangkeaw, S. Teeravitud, K.Bunyakiat, S. Ngamprasertsith, “Biofuel production from palm oil with supercritical alcohols: Effects of the alcohol to oil molar ratios on the biofuel chemical composition and properties,”Bioresource Technol.,vol. 102, pp. 10704–10710, 2011.
[34] C. Choi, J. Kim, C.Jeong, H. Kim, K. Yoo, “Transesterification kinetics of palm olein oil using supercritical methanol,”J. Supercrit. Fluid., vol. 58, pp. 365-370, 2011.
[35] I. Vieitez, C. Silva, I. Alkimim, G.R. Borges, F.C. Corazza, J.V. Oliveira, M.A. Grompone, I. Jachmanián, “Effect of temperature on the continuous synthesis of soybean esters under supercritical ethanol,”Energy & Fuels,vol. 23, pp. 558-563, 2009.
[36] I. Vieitez, C. Silva, G.R. Borges, F.C.Corazza, J.V. Oliveira, M.A. Grompone, I.Jachmanián, “Continuous production of soybean biodiesel in supercritical ethanol-water mixtures,”Energy & Fuels, vol. 22, pp. 2805-2809, 2008.
[37] A. Demirbas, “Biodiesel production via non-catalytic SCF method and Biodiesel fuel characteristics,”Energy Convers. Manag., vol. 47, pp. 2271-2282, 2006.
[38] I. Vieitez, C. Silva, I.Alkimim, G.R. Borges, F.C.Corazza, J.V. Oliveira, M.A.Grompone, I.Jachmanián, “Continuous catalyst-free methanolysis and ethanolysis of soybean oil under super critical alcohol/water mixtures,”Renew. Energ., vol. 35, pp. 1976–1981, 2010.
[39] A. Velez, G. Soto, P. Hegel, G. Mabe, S. Pereda, “Continuous production of fattya acid ethyl ésteresfrom sunflower oil using supercritical ethanol,” Fuel, vol. 97, pp. 703-709, 2012.